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MoCl5 as an effective chlorinating agent towards α-amino acids: synthesis of α-ammonium-acylchloride salts and α-amino-acylchloride complexes.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 6/7/2015, Vol. 44 Issue 21, p10030-10037, 8p
- Publication Year :
- 2015
-
Abstract
- The reactivity of MoCl<subscript>5</subscript> with α-amino acids was investigated for the first time by choosing CH<subscript>2</subscript>Cl<subscript>2</subscript> as the reaction medium. The interaction of MoCl<subscript>5</subscript> with l-proline proceeded with Cl/O interchange and led to the formation of [NH<subscript>2</subscript>(CH<subscript>2</subscript>)<subscript>3</subscript>CHC(O)Cl][MoOCl<subscript>4</subscript>], 1, in 63% yield. The reactions of MoCl<subscript>5</subscript> with l-phenylalanine, sarcosine, N,N-dimethylglycine and N,N-dimethyl-l-phenylalanine afforded the α-amino-acylchloride complexes MoOCl<subscript>3</subscript>[O=C(Cl)CH(R)N(R′)(R′′)] (R = CH<subscript>2</subscript>Ph, R′ = R′′ = H, 2a; R = R′ = H, R′′ = Me, 2b; R = H, R′ = R′′ = Me, 2c; R = CH<subscript>2</subscript>Ph, R′ = R′′ = Me, 2d), in ca. 70% yields. According to DFT studies, 2a,d are mononuclear Mo(v) octahedral complexes bearing a N,O-coordinated α-amino-acylchloride ligand. The presumed species formed during the first stages of the MoCl<subscript>5</subscript>/l-phenylalanine interaction were DFT-elucidated, thus the calculated Gibbs free energy profile for the multi-step reaction of MoCl<subscript>5</subscript> with l-phenylalanine was traced. [NH<subscript>3</subscript>CH(CH<subscript>2</subscript>Ph)C(O)Cl][MoOCl<subscript>4</subscript>], 3, acting as an intermediate in the course of the formation of 2a, was isolated by combination of [NH<subscript>3</subscript>CH(CH<subscript>2</subscript>Ph)C(O)Cl][Cl] with MoOCl<subscript>3</subscript>. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 44
- Issue :
- 21
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 102819673
- Full Text :
- https://doi.org/10.1039/c5dt01002k